Preparation method and application of a novel carbazole crystal sponge

Abstract

The application discloses a preparation method of a novel carbazole crystal sponge and application of the novel carbazole crystal sponge. The carbazole crystal sponge provided by the application has high stability in various common solvents; the prepared crystal sponge does not need to be activated; the successfully prepared crystal sponge can be directly used for soaking and testing the structure of a guest molecule, and a complex activation process is omitted, so that the operation is more convenient. The crystal sponge preparation method is simple, raw materials are easy to obtain, the method has good repeatability, high yield, and wide application range, and indicates a good application prospect.

Description

Technical Field

[0001] This invention relates to the field of crystal synthesis, and in particular to a novel method for preparing carbazole crystal sponges and their applications. Background Technology

[0002] Structural identification plays a crucial role in organic chemistry research. Identifying the structure of organic compounds is of great significance for studying their reactivity and biological activity. Currently, the combined use of various spectroscopic analyses is an important means of confirming molecular structure; however, these methods still cannot directly obtain the structure of organic molecules, and sometimes the predicted structure is even incorrect. Single-crystal X-ray diffraction (SCXRD) provides clear structural information at the atomic level and is the most direct and reliable method for determining molecular structure. However, SCXRD requires obtaining high-quality single crystals of suitable size, which seriously hinders the structural identification of some liquid, oily, and amorphous solid organic molecules.

[0003] Many researchers both domestically and internationally have designed and synthesized various "crystalline sponges." These sponges are prepared by immersing the organic molecules in a solution, causing the molecules to align regularly within the crystal. Single-crystal diffraction analysis is then performed to identify the organic molecules as the target molecules. For example, Fujita et al. reported a TPT-based crystalline sponge, Yaghi et al. synthesized the crystalline sponge MOF-520, and other researchers have reported the crystalline sponge BTB-MOF-24, suitable for the structural identification of long-chain compounds.

[0004] However, these reported crystalline sponges all require complex solvent exchange or activation processes, which are cumbersome and difficult to apply directly. The preparation of novel crystalline sponges with high stability, simple operation, and no activation requirement is of great significance for the structural identification of organic molecules. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings and deficiencies of the prior art and provide a carbazole crystal sponge for the structural identification of organic molecules.

[0006] Another object of the present invention is to provide a method for preparing the above-mentioned carbazole crystal sponge.

[0007] Another object of the present invention is to provide the application of the above-mentioned carbazole crystal sponge.

[0008] The objective of this invention is achieved through the following technical solution:

[0009] A carbazole compound, the structural formula of which is shown in Formula I:

[0010]

[0011] A carbazole crystal sponge with the chemical formula [Cu4I4C] for asymmetric units. 52 H 28 N6] n , where n is an integer.

[0012] The carbazole crystal sponge described is tetragonal, with space group I41 and cell parameters as follows: α=β=γ=90°, cell volume is

[0013] The molecular structure of the carbazole crystal sponge is shown in Formula II:

[0014]

[0015] The preparation method of the above-mentioned carbazole compound includes the following steps:

[0016] (1) Dissolve the raw material 3,6-dibromo-9H-carbazole in acetone, add KMnO4, heat and stir to react, then cool to room temperature, dissolve the precipitate with dichloromethane, repeat 3 times, combine the organic layers, concentrate under reduced pressure, and perform column chromatography on the residue obtained, elute with petroleum ether, collect all eluent to obtain the intermediate;

[0017] (2) The intermediate, 4-alkynylpyridine hydrochloride, diisopropylamine, tri-n-butylphosphine, cuprous iodide, and catalyst PdCl2(PhCN)2 were dissolved in tetrahydrofuran. The mixture was heated and stirred. After cooling to room temperature, the reaction solution was diluted with water and dichloromethane. The mixture was extracted three times with dichloromethane. The organic layers were combined, washed with bromine water and dried with Na2SO4. After recovering dichloromethane under reduced pressure, the residue was subjected to column chromatography. The mixture was eluted with a mobile phase gradient and concentrated under reduced pressure to obtain the carbazole compound.

[0018] The molar ratio of 3,6-dibromo-9H-carbazole to KMnO4 in step (1) is 1:2 to 3; preferably 1:2.5.

[0019] The heating and stirring reaction conditions described in step (1) are 35-45°C for 8-12 hours; preferably 40°C for 10 hours.

[0020] The column chromatography described in steps (1) and (2) is performed using a 200-mesh silica gel column.

[0021] The amount of acetone mentioned in step (1) is sufficient to completely dissolve the solute.

[0022] The amount of dichloromethane mentioned in step (1) is sufficient to completely dissolve the solute.

[0023] The molar ratio of the intermediate to 4-alkynylpyridine hydrochloride in step (2) is 1:6 to 10; preferably 1:8.

[0024] The heating and stirring reaction conditions described in step (2) are 40-80°C for 10-20 hours; preferably 40°C for 10 hours.

[0025] The elution in step (2) is performed using a mobile phase of CH2Cl2:CH3OH = 100:1, 80:1, 60:1, and the eluent of CH2Cl2:CH3OH = 60:1 is collected.

[0026] The preparation method of the above-mentioned carbazole crystal sponge includes the following steps:

[0027] (3) Dissolve the above carbazole compound in chloroform and place it in the lower layer. Dissolve cuprous iodide in acetonitrile and place it in the upper layer. Diffusion is carried out at room temperature, and carbazole crystal sponge is obtained by crystallization.

[0028] The molar ratio of the ligand to cuprous iodide in step (3) is 2:1 to 5; preferably 2:3.

[0029] The diffusion time described in step (3) is 5 to 10 days.

[0030] The above-mentioned carbazole compounds are used in the preparation of crystalline sponges.

[0031] The application of the above-mentioned carbazole compounds and / or carbazole crystal sponges in the structural identification of organic molecules.

[0032] The present invention has the following advantages and effects compared with the prior art:

[0033] (1) The prepared crystal sponge does not require activation. The successfully prepared crystal can be directly used to test the molecular structure of the guest, saving the complicated activation process and making the operation more convenient.

[0034] (2) The preparation method of the crystal sponge is simple, the raw materials are readily available, and the reproducibility is good with a high yield.

[0035] (3) This crystal sponge can be used not only for the structural identification of liquid natural products, but also for the structural identification of solid and mixtures.

[0036] This invention provides a new approach for the structural identification of organic molecules and expands the application of carbazole crystal sponges. Attached Figure Description

[0037] Figure 1This is the synthetic route for the ligand 3,3',6,6'-tetrakis(pyridin-4-ylethynyl)-9,9'-bicarbazole.

[0038] Figure 2 This is the proton NMR spectrum of the ligand 3,3',6,6'-tetrakis(pyridin-4-ylethynyl)-9,9'-bicarbazole.

[0039] Figure 3 This is the mass spectrum of the ligand 3,3',6,6'-tetrakis(pyridin-4-ylethynyl)-9,9'-bicarbazole.

[0040] Figure 4 This is a morphological image of the crystalline sponge prepared in Example 1.

[0041] Figure 5 This is a crystal structure diagram of the crystalline sponge prepared in Example 1.

[0042] Figure 6 This is a graph showing the stability test results of the carbazole crystal sponge in Example 6.

[0043] Figure 7 These are experimental results of the carbazole crystal sponge provided in Example 7 of the present invention, wherein: the chemical structure of 3,4-dimethoxyphenol (a), the asymmetric unit diagram of the crystal (b), the host-guest interaction diagram (c), and the unit cell packing diagram (d).

[0044] Figure 8 These are experimental results of the carbazole crystal sponge provided in Example 8 of the present invention, including: the chemical structure of 1,4-dimethoxybenzene (a), the asymmetric unit diagram of the crystal (b), the host-guest interaction diagram (c), and the unit cell packing diagram (d).

[0045] Figure 9 These are experimental results of the carbazole crystal sponge provided in Example 9 of the present invention, including: the chemical structure of cinnamaldehyde (a), the asymmetric unit diagram of the crystal (b), the host-guest interaction diagram (c), and the unit cell packing diagram (d).

[0046] Figure 10 These are experimental results of the carbazole crystal sponge provided in Example 10 of the present invention, including: chemical structure of benzyl salicylate (a), asymmetric unit diagram of the crystal (b), host-guest interaction diagram (c), and unit cell packing diagram (d).

[0047] Figure 11These are experimental results of the carbazole crystal sponge provided in Example 11 of the present invention, wherein: the chemical structure of resveratrol (a), the asymmetric unit diagram of the crystal (b), the host-guest interaction diagram (c), and the unit cell packing diagram (d). Detailed Implementation

[0048] The present invention will be further described in detail below with reference to the embodiments and accompanying drawings, but the embodiments of the present invention are not limited thereto.

[0049] Unless otherwise specified in the following implementation plan, the test conditions are generally as per standard test conditions or the test conditions recommended by the reagent company. Unless otherwise specified, all materials and reagents used are commercially available.

[0050] Example 1: Preparation of Carbazole Crystal Sponge

[0051] (1) Dissolve 1 g (3.08 mmol) of the starting material 3,6-dibromo-9H-carbazole in 10 mL of acetone, and add 7.7 mmol of KMnO4. Stir at 40 °C for 10 hours, then cool to room temperature. Dissolve the precipitate in 10 mL of dichloromethane, repeating the process three times. Combine the organic layers and concentrate under reduced pressure. Perform silica gel column chromatography (200 mesh, 60 g) on ​​the residue, elute with petroleum ether, and collect all the eluent to give the intermediate 3,3',6,6'-tetrabromo-9,9'-bicarbazole in 50.1% yield.

[0052] (2) 2.31 mmol of the intermediate, 18.48 mmol of 4-alkynylpyridine hydrochloride, diisopropylamine (12 ml), 705 μL of tri-n-butylphosphine, 26.4 mg of cuprous iodide, and 88.6 mg of catalyst PdCl2(PhCN)2 were dissolved in 40 mL of tetrahydrofuran. The reaction mixture was heated and stirred at 40 °C for 10 hours. After cooling to room temperature, the reaction solution was diluted with water and dichloromethane (ratio 1:3, total volume 80 ml), extracted three times with dichloromethane, and the organic layers were combined, washed with bromine water, and dried with Na2SO4. After recovering dichloromethane under reduced pressure, the residue was subjected to silica gel column chromatography (200 mesh, 60 g column, 3 cm diameter, 60 cm length), eluted with a mobile phase gradient (CH2Cl2:CH3OH = 100:1, 80:1, 60:1) (collecting the 60:1 eluent), concentrated under reduced pressure, and the ligand was obtained in a yield of 70.2%.

[0053] (3) In a test tube, 0.015 mmol of the ligand was dissolved in chloroform (4 mL) and placed in the lower layer. 0.01 mmol of cuprous iodide was dissolved in acetonitrile (3 mL) and placed in the upper layer. Diffusion was carried out at room temperature for 5 days to obtain crystallized sponges with a yield of 20% (see figure). The morphology of the crystal sponges is shown in the figure. Figure 4 .

[0054] The synthetic route for the ligand 3,3',6,6'-tetrakis(pyridin-4-ylethynyl)-9,9'-bicarbazole obtained in step (2) is shown below. Figure 1 The proton spectrum of the ligand is shown in [reference needed]. Figure 2 The NMR data are as follows: 1 ¹H NMR (400MHz, DMSO-d6) 8.65 (Ha), 7.55 (Hb), 8.80 (Hc) ppm, 7.10 (Hd, J = 8.0 Hz), 7.70 (He, J = 8.0 Hz). The mass spectra of the ligands are shown below. Figure 3 ,from Figure 3 It can be clearly observed that m / z = M + H] + =737.2451, [M+2H] 2+ The quasi-molecular ion peak is 369.1279, and its structural formula is shown in Formula I.

[0055]

[0056] The crystal obtained in step (3) was subjected to single-crystal X-ray diffraction analysis using an Agilent Gemini S ultra CCD diffractometer, and modeled and refined using OLEX2. The results showed that non-hydrogen atoms were anisotropically refined, and hydrogen atoms were fixed using a riding model, with the general structural formula shown in Formula II and the chemical formula [Cu4I4C]. 52 H 28 N6] n n is an integer. The obtained crystallographic parameters are shown in Table 1, and the crystal structure diagram is shown in [Table 1]. Figure 5 As can be seen from the image, this crystalline sponge has obvious cavities. It can be used to encapsulate guest molecules.

[0057]

[0058] Table 1 Crystal data of the novel carbazole crystal sponge

[0059]

[0060]

[0061] Example 2

[0062] (1) Dissolve 1 g (3.08 mmol) of the starting material 3,6-dibromo-9H-carbazole in 10 ml of acetone, add 2.5 equivalents of KMnO4, stir at 50 °C for 12 hours, then cool to room temperature, dissolve the precipitate in 10 ml of dichloromethane, repeat 3 times, combine the organic layers, and concentrate under reduced pressure. Perform silica gel column chromatography (200 mesh, 60 g) on ​​the residue, elute with petroleum ether (collect all eluent) to give the intermediate 3,3',6,6'-tetrabromo-9,9'-bicarbazole in 52.5% yield.

[0063] (2) 2.31 mmol of the intermediate (1 equivalent), 4-alkynylpyridine hydrochloride (8 equivalents), diisopropylamine (12 mL), tri-n-butylphosphine (705 μL), cuprous iodide (26.4 mg), and catalyst PdCl2(PhCN)2 (88.6 mg) were dissolved in 40 mL of tetrahydrofuran. The mixture was heated to 55 °C and stirred for 13 hours. After cooling to room temperature, the reaction solution was diluted with water and dichloromethane (ratio 1:3, total volume 80 mL), extracted three times with dichloromethane, and the organic layers were combined, washed with bromine water, and dried over Na2SO4. After recovering dichloromethane under reduced pressure, the residue was subjected to column chromatography (column diameter 3 cm, length 60 cm) with a mobile phase gradient elution (CH2Cl2:CH3OH = 100:1, 80:1, 60:1) (collecting the 60:1 eluent), concentrated under reduced pressure, and the ligand was obtained in a yield of 78.3%.

[0064] (3) In a test tube, 0.015 mmol of ligand was dissolved in chloroform (4 mL) and placed in the lower layer. 0.01 mmol of cuprous iodide was dissolved in acetonitrile (3 mL) and placed in the upper layer. Diffusion was carried out at room temperature for 6 days to obtain crystals of crystalline sponge with a yield of 22S.

[0065] The structure was identified according to the method in Example 1, and the results showed that the composition and structure were consistent with those of the crystalline sponge obtained in Example 1.

[0066] Example 3

[0067] (1) Dissolve 1 g (3.08 mmol) of the starting material 3,6-dibromo-9H-carbazole in 10 ml of acetone, add 2.5 equivalents of KMnO4, stir at 60 °C for 14 hours, then cool to room temperature, dissolve the precipitate in 10 ml of dichloromethane, repeat 3 times, combine the organic layers, and concentrate under reduced pressure. Perform silica gel column chromatography (200 mesh, 60 g) on ​​the residue, elute with petroleum ether (collect all eluent) to give the intermediate 3,3',6,6'-tetrabromo-9,9'-bicarbazole in 56.6% yield.

[0068] (2) Synthesis of 3,3',6,6'-tetrakis(pyridin-4-ylethynyl)-9,9'-bicarbazole ligand: 2.31 mmol of the intermediate (1 equivalent), 4-alkynylpyridine hydrochloride (8 equivalents), diisopropylamine (12 ml), tri-n-butylphosphine (705 μL), cuprous iodide (26.4 mg), and catalyst PdCl2(PhCN)2 (88.6 mg) were dissolved in 40 mL of tetrahydrofuran. The mixture was heated to 65 °C and stirred for 16 hours. After cooling to room temperature, the reaction solution was diluted with water and dichloromethane (1:3 ratio, total volume 80 ml), extracted three times with dichloromethane, and the organic layers were combined, washed with bromine water, and dried over Na2SO4. After recovering dichloromethane under reduced pressure, the residue was subjected to column chromatography (column diameter 3 cm, length 60 cm), eluted with a mobile phase gradient (CH2Cl2:CH3OH = 100:1, 80:1, 60:1) (collecting the 60:1 eluent), concentrated under reduced pressure, and the ligand was obtained in a yield of 79.6%.

[0069] (3) Synthetic crystal sponge

[0070] In a test tube, 0.015 mmol of the ligand was dissolved in chloroform (4 mL) and placed in the lower layer. 0.01 mmol of cuprous iodide was dissolved in acetonitrile (3 mL) and placed in the upper layer. Diffusion was carried out at room temperature for 8 days to obtain crystals of crystalline sponge with a yield of 26S.

[0071] Experimental analysis confirmed that the composition and structure of the crystalline sponge obtained in Example 1 were consistent with those of the sponge obtained in Example 1.

[0072] Example 4

[0073] (1) Dissolve 1 g (3.08 mmol) of the starting material 3,6-dibromo-9H-carbazole in 10 ml of acetone, add 2.5 equivalents of KMnO4, stir at 70 °C for 18 hours, then cool to room temperature, dissolve the precipitate in 10 ml of dichloromethane, repeat 3 times, combine the organic layers, and concentrate under reduced pressure. Perform silica gel column chromatography (200 mesh, 60 g) on ​​the residue, elute with petroleum ether (collect all eluent) to give the intermediate 3,3',6,6'-tetrabromo-9,9'-bicarbazole in 62.5% yield.

[0074] (2) Synthesis of 3,3',6,6'-tetrakis(pyridin-4-ylethynyl)-9,9'-bicarbazole ligand: 2.31 mmol of the intermediate (1 equivalent), 4-alkynylpyridine hydrochloride (8 equivalents), diisopropylamine (12 ml), 705 μL of tri-n-butylphosphine, 26.4 mg of cuprous iodide, and 88.6 mg of catalyst PdCl2(PhCN)2 were dissolved in 40 mL of tetrahydrofuran. The mixture was heated to 75 °C and stirred for 19 hours. After cooling to room temperature, the reaction solution was diluted with water and dichloromethane (ratio 1:3, total volume 80 ml), extracted three times with dichloromethane, and the organic layers were combined, washed with bromine water, and dried over Na2SO4. After recovering dichloromethane under reduced pressure, the residue was subjected to column chromatography (column diameter 3 cm, length 60 cm), eluted with a mobile phase gradient (CH2Cl2:CH3OH = 100:1, 80:1, 60:1) (collecting the 60:1 eluent), concentrated under reduced pressure, and the ligand was obtained in a yield of 83.4%.

[0075] (3) Synthetic crystal sponge

[0076] In a test tube, 0.015 mmol of the ligand was dissolved in chloroform (4 mL) and placed in the lower layer. 0.01 mmol of cuprous iodide was dissolved in acetonitrile (3 mL) and placed in the upper layer. Diffusion was carried out at room temperature for 9 days to obtain crystals of crystalline sponge with a yield of 28%.

[0077] Experimental analysis confirmed that the composition and structure of the crystalline sponge obtained in Example 1 were consistent with those of the sponge obtained in Example 1.

[0078] Example 5

[0079] (1) 1 g (3.08 mmol) of the starting material 3,6-dibromo-9H-carbazole was dissolved in 10 ml of acetone, and 2.5 equivalents of KMnO4 were added. The mixture was stirred at 80 °C for 20 hours, then cooled to room temperature. The precipitate was dissolved in 10 ml of dichloromethane, and the reaction was repeated three times. The organic layers were combined and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography (200 mesh, 60 g), and eluted with petroleum ether (collecting all eluent) to give the intermediate 3,3',6,6'-tetrabromo-9,9'-bicarbazole in 65.6% yield.

[0080] (2) 2.31 mmol of the intermediate (1 equivalent), 4-alkynylpyridine hydrochloride (8 equivalents), diisopropylamine (12 mL), tri-n-butylphosphine (705 μL), cuprous iodide (26.4 mg), and catalyst PdCl2(PhCN)2 (88.6 mg) were dissolved in 40 mL of tetrahydrofuran. The mixture was heated to 80 °C and stirred for 20 hours. After cooling to room temperature, the reaction solution was diluted with water and dichloromethane (1:3 ratio, total volume 80 mL), extracted three times with dichloromethane, and the organic layers were combined, washed with bromine water, and dried over Na2SO4. After recovering dichloromethane under reduced pressure, the residue was subjected to column chromatography (column diameter 3 cm, length 60 cm) with a mobile phase gradient elution (CH2Cl2:CH3OH = 100:1, 80:1, 60:1) (collecting the 60:1 eluent), concentrated under reduced pressure, and the ligand was obtained in 85.5% yield.

[0081] (3) In a test tube, 0.015 mmol of ligand was dissolved in chloroform (4 mL) and placed in the lower layer. 0.01 mmol of cuprous iodide was dissolved in acetonitrile (3 mL) and placed in the upper layer. The solution was diffused at room temperature for 10 days to obtain crystals of crystalline sponge with a yield of 30%.

[0082] Experimental analysis confirmed that the composition and structure of the crystalline sponge obtained in Example 1 were consistent with those of the sponge obtained in Example 1.

[0083] Example 6: Stability Study of Carbazole Crystal Sponge

[0084] The crystalline sponge obtained in Example 1 was immersed in cyclohexane, chloroform, toluene, tetrahydrofuran, dimethyl sulfoxide, dimethylformamide, water, and acetonitrile. It was found that the carbazole crystalline sponge showed good stability in cyclohexane, chloroform, toluene, and tetrahydrofuran, maintaining its morphology unchanged after 3 and 48 hours. However, in dimethyl sulfoxide, dimethylformamide, water, and acetonitrile, the carbazole crystalline sponge remained stable only for 3 hours; by 48 hours, the color and morphology of the crystalline sponge had changed significantly. Figure 6 As shown, the crystalline sponge prepared by this invention can maintain good stability in a variety of solvents.

[0085] Example 7: Carbazole crystal sponge used for structural identification of 3,4-dimethoxyphenol

[0086] The crystalline sponge prepared in Example 1 was placed into a 1.5 ml liquid chromatography vial, and 200 μL of liquid natural product 3,4-dimethoxyphenol was added. The vial was capped and sealed, and then soaked at room temperature for 3 days.

[0087] Select a crystal of suitable size, approximately 0.2 mm × 0.08 mm × 0.04 mm, and then collect diffraction data using an Agilent Gemini SMILtraCCD diffractometer. The diffraction was performed at a low temperature of 150 K using Cu Kα. Diffraction data were acquired under X-ray conditions. The diffraction data were then reconstructed using the CrysAlisPro package. The reconstructed diffraction data were analyzed using the direct method in the SHEXLE package, and the structure was determined based on F... 2 The coordinates of each atom were refined using a full-matrix least-squares method. Except for solvent molecules, all non-hydrogen atoms were anisotropically modified. The refinement results are shown in Table 2, and the single-crystal X-ray diffraction results for this example are shown in [Table 2]. Figure 7 The chemical structure of 3,4-dimethoxyphenol is shown in (a) and its ORTEP diagram (b), along with the asymmetric unit of the crystal (c) and its crystal packing diagram (d).

[0088] Table 2: Crystal data of the crystalline sponge@3,4-dimethoxyphenol complex obtained after soaking the crystalline sponge in 3,4-dimethoxyphenol.

[0089]

[0090]

[0091] Experimental results demonstrate that the carbazole crystal sponge prepared in Example 1 can stably encapsulate the target object, and obtain the single-crystal structure of the object-encapsulated crystal, thus determining the structure of the object molecule. The operation is convenient and highly accurate.

[0092] Example 8: Carbazole crystal sponge used for structural identification of 1,4-dimethoxybenzene

[0093] The crystalline sponge prepared in Example 1 was placed in a 1.5 ml liquid chromatography vial, and 200 μL of 1,4-dimethoxybenzene tetrahydrofuran was added. The vial was capped and sealed, and then soaked at room temperature for 3 days. Crystals of suitable size (approximately 0.2 mm × 0.05 mm × 0.04 mm) were selected, and diffraction data were collected using an Agilent Gemini SMILtra CCD diffractometer. The diffraction was performed at a low temperature of 120 K using Cu Kα... Diffraction data were acquired under X-ray conditions. The diffraction data were then reconstructed using the CrysAlisPro package. The reconstructed diffraction data were analyzed using the direct method in the SHEXLE package, and the structure was determined based on F... 2 The coordinates of each atom were refined using a full-matrix least-squares method. Except for solvent molecules, all non-hydrogen atoms were anisotropically treated. The refinement results are shown in Table 3, and the single-crystal X-ray diffraction results for this example are shown in [Table 3]. Figure 8 Chemical structure of 1,4-dimethoxybenzene (a) and ORTEP diagram (b), asymmetric unit of crystal (c) and crystal packing diagram (d).

[0094] Table 3: Crystal data of the crystalline sponge@1,4-dimethoxybenzene complex obtained after soaking the crystalline sponge in a tetrahydrofuran solution of 1,4-dimethoxybenzene.

[0095]

[0096]

[0097] Example 9: Carbazole crystal sponge for structural identification of cinnamaldehyde

[0098] The crystalline sponge prepared in Example 1 was placed in a 1.5 ml liquid chromatography vial, and 100 μL of liquid natural product cinnamaldehyde was added. The vial was capped and sealed, and then soaked at room temperature for 3 days. Crystals of suitable size (approximately 0.3 mm × 0.05 mm × 0.05 mm) were selected, and diffraction data were collected using an Agilent Gemini SMILtra CCD diffractometer. The diffraction was performed at a low temperature of 170 K using Cu Kα... Diffraction data were acquired under X-ray conditions. The diffraction data were then reconstructed using the CrysAlisPro package. The reconstructed diffraction data were analyzed using the direct method in the SHEXLE package, and the structure was determined based on F... 2 The coordinates of each atom were refined using a full-matrix least-squares method. Except for solvent molecules, all non-hydrogen atoms were anisotropically modified. The refinement results are shown in Table 4, and the single-crystal X-ray diffraction results for this example are shown in [Table 4]. Figure 9 Chemical structure of linalool (a) and ORTEP diagram (b), asymmetric unit of crystal (c) and crystal packing diagram (d).

[0099] Table 4: Crystal data of the crystal sponge@cinnamaldehyde complex obtained after soaking the crystal sponge in cinnamaldehyde.

[0100]

[0101]

[0102] Example 10: Carbazole crystal sponge for structural identification of benzyl salicylate.

[0103] The crystalline sponge prepared in Example 1 was placed in a 1.5 ml liquid chromatography vial, and 200 μL of benzyl salicylate was added. The vial was capped and sealed, and then soaked at room temperature for 3 days. Crystals of suitable size (approximately 0.3 mm × 0.04 mm × 0.03 mm) were selected, and diffraction data were collected using an Agilent Gemini SMILtra CCD diffractometer. The diffraction was performed at a low temperature of 150 K using Cu Kα... Diffraction data were acquired under X-ray conditions. The diffraction data were then reconstructed using the CrysAlisPro package. The reconstructed diffraction data were analyzed using the direct method in the SHEXLE package, and the structure was determined based on F... 2 The coordinates of each atom were refined using a full-matrix least-squares method. Anisotropy was applied to all non-hydrogen atoms, except for solvent molecules. The refinement results are shown in Table 5, and the single-crystal X-ray diffraction results for this example are shown in [Table 5]. Figure 10 Chemical structure (a) and ORTEP diagram (b) of benzyl salicylate, asymmetric unit (c) of the crystal and crystal packing diagram (d).

[0104] Table 5: Crystal data of the crystal sponge@benzyl salicylate complex obtained after soaking the crystal sponge in levorotatory borneol.

[0105]

[0106]

[0107] Example 11: Carbazole crystal sponge used for the structural identification of resveratrol

[0108] The crystalline sponge prepared in Example 1 was placed in a 1.5 ml liquid chromatography vial, and 200 μL of resveratrol was added. The vial was capped and sealed, and then soaked at room temperature for 3 days. Crystals of suitable size (approximately 0.3 mm × 0.06 mm × 0.04 mm) were selected, and diffraction data were collected using an Agilent Gemini SMILtra CCD diffractometer. The diffraction was performed at a low temperature of 150 K using CuKα... Diffraction data were acquired under X-ray conditions. The diffraction data were then reconstructed using the CrysAlisPro package. The reconstructed diffraction data were analyzed using the direct method in the SHEXLE package, and the structure was determined based on F... 2 The coordinates of each atom were refined using a full-matrix least-squares method. Anisotropy was applied to all non-hydrogen atoms except for solvent molecules. The refinement results are shown in Table 6, and the single-crystal X-ray diffraction results for this example are shown in [Table 6]. Figure 11Chemical structure of resveratrol (a) and ORTEP diagram (b), asymmetric unit of crystal (c) and crystal packing diagram (d).

[0109] Table 6: Crystal data of the crystalline sponge@resveratrol complex obtained after soaking the crystalline sponge in resveratrol.

[0110]

[0111]

[0112] The experimental results show that the crystalline sponge prepared by this invention can be used to analyze the crystal structure of various molecules that are difficult to identify using conventional methods. No activation is required; the successfully prepared crystals can be directly used to test the guest molecule structure, eliminating the complex activation process and making the operation more convenient. This crystalline sponge preparation method is simple, uses readily available raw materials, has good reproducibility, and high yield, showing broad application prospects in molecular structure identification.

[0113] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A carbazole compound, characterized in that... The structural formula is shown in Formula I: Formula I.

2. A carbazole crystal sponge, characterized in that: The carbazole crystal sponge described above has a molecular structure as shown in Formula II, where n is an integer greater than or equal to 1: Formula II; The chemical formula of the asymmetric unit in the carbazole crystal sponge is [Cu4I4C]. 52 H 28 N6] n , where n is an integer greater than or equal to 1; The carbazole crystal sponge described is tetragonal, with space group I41, and cell parameters: a=b= 22.0771(8) Å, c=40.593(2) Å, α = β = γ = 90°, and cell volume of 19784.8(17) Å. 3 .

3. The method for preparing the carbazole compound according to claim 1, characterized in that... Includes the following steps: (1) Dissolve the raw material 3,6-dibromo-9H-carbazole in acetone, add KMnO4, heat and stir to react, then cool to room temperature, dissolve the precipitate with dichloromethane, repeat 3 times, combine the organic layers, concentrate under reduced pressure, and perform column chromatography on the residue obtained, elute with petroleum ether, collect all eluent to obtain the intermediate; (2) The intermediate, 4-alkynylpyridine hydrochloride, diisopropylamine, tri-n-butylphosphine, cuprous iodide, and catalyst PdCl2(PhCN)2 were dissolved in tetrahydrofuran. The reaction was heated and stirred. After cooling to room temperature, the reaction solution was diluted with water and dichloromethane. The solution was extracted three times with dichloromethane. The organic layers were combined, washed with bromine water and dried with Na2SO4. After recovering dichloromethane under reduced pressure, the residue was subjected to column chromatography. The residue was eluted with a mobile phase gradient and concentrated under reduced pressure to obtain the carbazole compound.

4. The preparation method according to claim 3, characterized in that: The molar ratio of 3,6-dibromo-9H-carbazole to KMnO4 in step (1) is 1:2-3; The molar ratio of the intermediate in step (2) to 4-alkynylpyridine hydrochloride is 1:6 to 10.

5. The preparation method according to claim 3, characterized in that: The heating and stirring reaction conditions described in step (1) are 35-45℃ and stirring for 8-12 hours; The column chromatography described in steps (1) and (2) is performed using a 200-mesh silica gel column. The amount of acetone mentioned in step (1) is sufficient to completely dissolve the solute; The amount of dichloromethane mentioned in step (1) is sufficient to completely dissolve the solute; The heating and stirring reaction conditions described in step (2) are 40-80℃ and stirring for 10-20 hours; The elution in step (2) is performed using a mobile phase with CH2Cl2: CH3OH = 100:1, 80:1, and 60:1, and the eluent in the CH2Cl2: CH3OH = 60:1 portion is collected.

6. The method for preparing the crystalline sponge according to claim 2, characterized in that... Includes the following steps: The carbazole compound of claim 1 is dissolved in chloroform and placed in the lower layer. Cuprous iodide is dissolved in acetonitrile and placed in the upper layer. Diffusion is carried out at room temperature, and carbazole crystal sponge is obtained by crystallization.

7. The preparation method according to claim 6, characterized in that: The molar ratio of the carbazole compound to cuprous iodide is 2:1 to 5; The diffusion time is 5 to 10 days.

8. The application of the carbazole crystal sponge according to claim 2 in the structural identification of organic molecules; The organic molecules include at least one of 3,4-dimethoxyphenol, 1,4-dimethoxybenzene, cinnamaldehyde, benzyl salicylate, and resveratrol.

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